Glyoxalidine salts of long chain dicarboxylic acids



' GLYOXALIDINE SALTS or LONG CHAIN DICARBOXYLIC ACIDS v Aaron Sterlin, Chicago, 111., assignor to National Aluminate Corporation, Chicago, 11]., a corporation of Delaware l 1 No Drawing. Application April 2, 1952,

SerialNo. 280,197 Y 7 Claims. (Cl. 260309.6)

This invention relates to new chemical compounds and their use in hydrocarbon liquids, more particularly gasoline, diesel fuel oil, and furnace oils, and to a method of inhibiting corrosion of ferrous metals caused by the presence of water in such liquids.

Various attempts have been made to inhibit corrosion of ferrous metals in contact with hydrocarbon liquids such as gasoline and other hydrocarbon fuels Where the tendency to cause such corrosion has been due to the presence of small amounts of water. In many cases, even though a particular chemical is effective in inhibiting corrosion the amount required may be so large as to cause other adverse or harmful effects. For example, in gasoline the presence of a corrosion inhibitor may cause gum formation.

One of the objects of the present invention is to provide a hydrocarbon liquid which is inhibited against corrosion by the presence of a very small amount of an inhibiting agent which does not otherwise adversely 'aifect the properties of said hydrocarbon liquid.

A further object of the invention is to provide new chemical compounds which are eliective for this purpose.

A still further object of the invention is to provide a neW and improved method of treating ferrous metals to prevent corrosion caused by Water. Other objects will appear hereinafter.

In accomplishing these objects in accordance with this invention, new compounds have been prepared which can be described broadly as aliphatic carboxylic acid salts of a glyoxalidine and an organic aliphatic dicarboxylic acid containing at least 10 carbon atoms, preferably l'to 36 carbon atoms, wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the'carbon atom in the 4-position is linked to a member from'thefgroup consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, the carbon'atom in the 5-position is linked to a member from thegroup consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, there being at least one hydrogen atom attached to said nitrogen atom.

These compounds can also be characterized as monoglyoxalidine salts of said organic aliphatic dicarboxylic acids or diglyoxalidine salts of such acids, depending upon 1 whether one or two mols of the glyoxalidine is reacted with the organic aliphatic dicarboxylic acid. If only one mol. of the glyoxalidine is reacted the resultant compound is a monoamine salt containing a free carboxylic acid.

group. If two mols of the glyoxalidine are reacted the resultant compound is a diarnine salt. The glyoxalidines employed as starting materials are made by well known procedures by reacting a fatty acid with an aliphatic poly-i amine with the elimination of water as described, for example, in Wilson, U. s. Patent No. 2,267,965 and Wilkes et al., U. S. Patent No. 2,268,273. 1

The glyoxalidines with which the presentinvention is particularly concerned are those in which the glyoxalidine.

portion of the molecule is derived by reacting together one of the acids from the group consisting of lauric acid,

myristic acid, palmitic acid, oleic acid and stearic acid,

with an aliphatic polyamine from the group consisting of aminoethylethanolamine, diethylenetriamine and triethyl-" enetetramine. When the glyoxalidine is derived fromaminoethylethanolamine the resultant product contains a hydroxyethyl group in the l-position. When'the gly-. oxalidine is derived from diethylenetriamine the resultant product contains an aminoethyl group in the l position, and when the glyoxalidine is derived from triethylenetetramine the resultant product contains a (2-aminoethyl)- aminoethyl group in the l-position.

The number of carbon atoms in the 'aliphatichydro carbon group in the 2-position is always one less than that in the aliphatic carboxylic acid from which the glyoxalidine is derived. Thus, if the glyoxalidine is made from lauric acid the hydrocarbon group in the 2-position will contain 11 carbon atoms. If the glyoxalidine is made from oleic acid .the hydrocarbon group in the 2-position will be a heptadecenyl group containing 17 carbon atoms; The hydrocarbon group in the 2-position preferably contains 13 to 17 carbon atoms for the purpose of the present invention. i

Specific examples of glyoxalidines that can be reacted with sebacic acid, dilinoleic acid and other long chain organic aliphatic dicarboxylic acids in preparing salts suitable for the purpose of the invention are: 1-(2-hydroxyethyl) 2 undecyl glyoxalidine, l-(2-hydroxyethyD-2-tridecyl glyoxalidine, l-(2-hydroxyethyl)-2-pentadecyl glyoxalidine, l-(2-hydroxyethyl)-2-heptadecyl glyoxalidine, l (2 hydroxyethyl) 2 heptadecenyl glyoxalidine, l-(2 aminoethyD-Z-undecyl glyoxalidine, I-(Z-amin e'thyD-Z- tridecyl glyoxalidine, 1-(2-aminoethyl)-2-pentadecyl gly'-. oxalidine, 1-(Z-aminoethyl)-2-heptadecyl glyoxalidine, l-

ethyD-aminoethyl]-2-heptadecenyl glyoxalidine, 4-methyl- Z-undecyl glyoxalidine, 4-methyl-2-tridecyl glyoxalidine, 4-methyl-2-pentadecyl glyoxalidine, 4-methyl-2-heptadecy'l" glyoxalidine, 4-methyl-2-heptadecenyl glyoxalidine.

The organic aliphatic dicarboxylic acid salts are prepared by mixing a glyoxalidine of the type described-ar d an organic aliphatic dicarboxylic acid of the type described in mol ratios of 1:1 in caseit is desired to pre pare the monoamine salt, or 2:1 in case it is desired to prepare the diamine salt, and warming the reaction mixture at temperatures sufiicient to melt the dicarboxylic acid if it is a solid for 5 to 15 minutes with or without a catalyst until homogeneous materials are obtained.

In the practice .of the invention it has been found that especially good results in inhibiting corrosion in gasoline 2 containing water have been obtained by employing as the corrosion inhibiting agent the reaction products of sebacic acid and I-(Z-hydroxy ethyl)-2-heptadecenyl glyoxalidine. Especially good results have been obtained with the. reaction product derived by reacting two mols ox-alidine with one mol of sebacic acid.

In order to evaluate the invention tests were made in? hydrocarbon fuels to which water had been added.

The organic aliphatic dicarboxylic acid salt of the gly-- oxalidine of the type previously describedwas prepared for use as a 10% by weight concentrate in a'sm'table solvent.

The test specimens were hot rolled mild steel rods Patented Dec. 11, 1-956 of said gly- A" x2%-' "of whiclra 2%" length was polished with #3/0 emerycloth The test medium, for example, gasoline, was placed in a 25 x 150 mm. screw cap tube. To 40 ml. of the test medium were added-first the" inhibitor solutionpreviously described and after mild agitation 10%: by volume of distilled-water which: had beenequilibrated with air. The capped tubewas then mechanically agitated at room'tempe1'ature (75'* F.-)' forsix hours by'end over end tumbling; The test solution was-then transferred to a numbered 25 X 150 mm; test tube and the water and hydrocarbon phase: were: permitted to separate; The test specimen wasiinsertedin thetubeso that a part'was exposed to the lowen phase'-(water) withoutcontacting any part of'the' container. The tube' was not disturbed for the 72-hour" test :duration:

Otherstests' wereset up-as described above with selected materialstih whiclr.1 %-:Water instead of 10% was used.

After completion ofthetest the specimen was removed, rinsedi-Withacetone. and-air dried. It was then evaluated on the extent of visible corrosion. Each test was made induplicatez. Ifrboth specimens were not visibly corroded the. materialnwas classed as efiective and if both appeared to be: corroded. the material was called ineffective. Wherevenone: of 'the pairs was'uncorroded and the other corroded-the-;testiswasrepeated; If, after retesting, either specimen-wascorroded the material was judged to be inefiective at the. tested concentration. This criterion is identicalwith'that used in ASTM D665-49T. V

Thea-following examples illustrate someof the results obtained when compositions falling within the scope of the invention were evaluated in the manner just described.

Example I The,.,se bacic acid salt derived by reacting two mols of 1-(2 -hydroxyethyl)-2-heptadecenylglyoxalidine with one mol of-- sebacicacid at, a temperature of about 133 C. for about.5 to. 15 minutes whentested under the foregoingconditions; in Standard Red Crown gasoline to which l%ldistilled water had been added was efiective in inhibiting corrosion, of thetest specimens at concentrations ofQlO parts of said-amine salt. per million parts of gasoline in a series ofsixtests.

Ina series of, three testsat a. concentration of- 25 parts per million the said: glyoxalidine Sebacic-acid salt completely inhibited corrosion under. the test conditions described.

Ina series. of six tests at a concentration of 5 partsper million in said. gasoline under the sametest conditions there was slight tomoderatecorrosion of thetest specimens;

Example 11 When'the same corrosion inhibiting composition was tested under. agitated conditions according to ASTM method D6 65.49,T using room temperature instead of 140. F. andistrips of SAE-lOlS steel instead of SAE- 1020*or'SAE-1025"steel theaforesaid diglyoxalidine' sebacic acid salt wasefiective in preventing corrosion at a concentration of' 0.31 part per millionin the gasoline.

V V Example-III .Under the: same test conditions as in Example II at a concentration of 0.16 part per million inthe gasoline Results; similarg to those: in llxample I were obtained; withethe-ireactioni'product"derived-by reacting-one m'ol of I-(Z-hydroxy ethyl)-2 heptadecenyl glyoxalidine with-'one mol of sebacic acid at a temperature of about 133 C.

for "about'5' to 15 minutes;

Example V The monoamine salt of a dimer acid was prepared by heatin together at a temperature up to 100 F. equimolecular proportions of 1-(2-hydroxy ethyl)-2-heptadecenyl glyo'xalidine and a dimer acid containing about by weight of-dilinoleic acid. This product was effective in inhibiting corrosion in a gasoline-watersystem under the test conditions. previously desoribedrat a concentration of 25 parts per million.

Example. VI

The solvent which is-used todissolve the active effective ingredient is subject to some variation depending upon the. solubility characteristics of the particular compound employed. In'somecases, even though the corrosion i117- hibiting. compound is insolublein a particular solvent itwilldissolve in acombinationof solvents. For instance, the, compound tested in Example I denatured-ethyl-alcohol, soluble in Indocene (a petroleum. fraction highinaromaticcompounds and naphthenes) soluble in,99% isopropanol, insoluble in virgin gas oil and. soluble in xylene. This product dissolvessatisfactorily in a mixture of xylene and naphtha.

lowing composition:

Ingredients Weight percent Sebacic acid salt of Example I 12 Xylene 35 Naphtha: (flash point 80 to 105 F.) 53

Similarly other. compositions can be prepared using,

suitable solvents.

It will be understood that the efiective corrpsionin-v.

hibiting. ingredient can be added directly 'to' the hydro carbon liquid provided it is soluble therein. However,

the amounts required are so small that it is preferable to prepare. a solution of the active ingredient containing about 5 to about 15% thereof, the remainder being a suitable solvent which dissolves the corrosion" inhibiting ingredient and is. miscible, with the medium to which the solution is to be'added.

It willbe' understood that some vanations can bemade: in the preparation of the. corrosion inhibiting chemicals and in the'procedures employed in using such chemicals.

glyoxalidines previously. described there may; be mentioned theacids known. in the trade as VR fatty acid and VR.-l acid. VR fatty acid is an organic carboxy acidfmaterial which is a vegetable residue resulting fromthe distillation of soap stock. This material contains ester bodies and has the following characteristics:

Acid value 45 Saponification-;value c a a I50 Iodine; value"; Color: (Bartlett) 13" Viscosity (ZahnGsat 75'C.);. SCO11dS l5 VR-l acid is a mixture ofvpolybasic acids with an average molecular 'weight of about 1000. It has an average of.

slightlydess than twocarboxylic acid groups per moleculei It-isfa. by-product' from theproduction. of SGbQGiQ, acid? 'bYT-hl," caustic fus'ioniofjcastor oil, consists'princi;

pally of""polymeri2ed linoleic acid, contains dimerized,

trimerize'd,an'd higherpolymerized linoleic acid, and is is soluble in 100% As an illustration, Where the corrosioninhibiting'ingredient is to be added to gasoline a suitable concentrate has the'fol A s v examples of other chain aliphatic di-- carboxylic acids which can be reacted withany of the:

a dark amber, rather viscous liquid. A typical sample of VR-l acid has the following analysis:

One of the important advantages of the present invention is that the addition of the compositions herein described to gasoline in the quantities which are effective in inhibiting corrosion has no adverse effects such as gum formation. In actual tests using a corrosion inhibiting composition consisting of 12% by weight of the product obtained by reacting two mols of 1-(2-hydroxy ethyl)-2-heptadecenyl glyoxalidine with one mol of sebacic acid, 35% by weight Xylene and 53% by weight of naphtha, there was a decrease in gum formation in the gasoline from 2.8 mg. per 100 ml. to 1.0 mg. per 100 ml. at a concentration of 10 parts of the corrosion inhibiting chemical (84 parts of the solvent solution of said chemical) per million parts by weight of gasoline.

The term glyoxalidine refers to a compound having the following structural formula wherein R is an aliphatic hydrocarbon radical; R, Y and Z are either hydrogen or an aliphatic group, it being understood that for the purpose of the present invention R, R, Y and Z are further restricted in the manner previously described. It should also be noted that in the preferred compounds of the present invention R is composed of carbon and hydrogen atoms, Y and Z are either hydrogen or groups consisting of carbon and hydrogen, and R is either hydrogen, a group consisting of carbon and hydrogen, a group consisting of carbon, hydrogen and nitrogen, or a group consisting of carbon, hydrogen and oxygen. In other Words, in the preferred compounds with respect to R the atoms in the group are selected from the group consisting of hydrogen, carbon, nitrogen and oxygen.

The invention is hereby claimed as follows:

1. Salts of an organic aliphatic dicarboxylic acid containing at least 10 carbon atoms in a hydrocarbon structure and a glyoxalidine wherein the carbon atom in the 2-position is linked to a higher aliphatic hydrocarbon group containing at least 8 carbon atoms, the carbon atom in the 4-position is linked to a member from the group consisting of hydrogen and lower aliphatic hydro carbon groups containing not more than 6 carbon atoms, the carbon atom in the 5-position is linked to a member from the group consisting of hydrogen and lower aliphatic hydrocarbon groups containing not more than 6 carbon atoms, there being at least one hydrogen atom on each of the carbon atoms in the 4- and 5-positions, and the nitrogen atom in the 1-position is linked to a member from the group consisting of hydrogen and lower aliphatic groups containing not more than 6 carbon atoms, said last named lower aliphatic groups being composed of atoms from the group consisting of hydrogen, carbon, nitrogen and oxygen.

2. A sebacic acid salt of I-(Z-hydroxy ethyl)-2-heptadecenyl glyoxalidine.

3. The diglyoxalidine acid salt of 1-(2-hydroxy ethyl)- Z-heptadecenyl glyoxalidine and sebacic acid.

4. A composition of matter having the following structural formula wherein A is a polymerized linoleic acid.

5. A composition of matter having the following structural formula wherein A is dilinoleic acid.

6. A composition of matter having the following structural formula wherein A is a polymerized linoleic acid.

7. A composition of matter having the following structural formula wherein A is dilinoleic acid.

References Cited in the file of this patent UNITED STATES PATENTS 2,324,491 De Groote July 20, 1943 2,374,354 Kaplan Apr. 24, 1945 2,466,530 Blair et a1. Apr. 5, 1949 2,514,508 Nunn July 11, 1950 2,520,102 Tryon Aug. 22, 1950 2,528,380 Mannheimer Oct. 31, 1950 2,553,183 Caron et a1 May 15, 1951 2,646,399 Hughes July 21, 1953 2,659,731 Luvisi Nov. 17, 1953 

1. SALTS OF AN ORGANIC ALIPHATIC DICARBOXYLIC ACID CONTAINING AT LEAST 10 CARBON ATOMS IN A HYDROCARBON STRUCTURE AND A GLYOXALIDINE WHEREIN THE CARBON ATOM IN THE 2-POSITION IS LINKED TO A HIGHER ALIPHATIC HYDROCARBON GROUP CONTAINING AT LEAST 8 CARBON ATOMS, THE CARON ATOM IN THE 4-POSITION IS LINKED TO A MEMBER FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALIPHATIC HYDROCARBON GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, THE CARBON ATOM IN THE 5-POSITION IS LINKED TO A MEMBER FROM THE GROUP CONSISTING OF HYDROGEN AND LOWER ALIPHATIC HYDROCARBON GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, THERE BEING AT LEAST ONE HYDROGEN ATOM ON EACH OF THE CARBON ATOMS IN THE 4- AND 5-POSITIONS, AND THE NITROGEN ATOM IN THE 1-POSITION IS LINKED TO A MEMBER FROM THE GROUP CONSISTING HYDROGEN AND LOWER ALIPHATIC GROUPS CONTAINING NOT MORE THAN 6 CARBON ATOMS, SAID LAST NAMED LOWER ALIPHATIC GROUPS BEING COMPOSED OF ATOMS FROM THE GROUP CONSISTING OF HYDROGEN, CARBON, NITROGEN AND OXYGEN. 